KR101113472B1 - Laminate comprising polycarbonate resin - Google Patents

Abstract

According to the present invention, there is provided a laminate having a substrate containing a polycarbonate resin and a layer containing an acrylic resin, wherein a layer containing the acrylic resin is formed on the surface of the substrate containing the polycarbonate resin by coextrusion. The thickness of the layer containing this acrylic resin is 20-120 micrometers, The total thickness of the laminated body is 0.3-1.5 mm, The surface of the layer containing this acrylic resin is hard-coated, The said acrylic resin is It is a copolymer of methyl methacrylate and acrylic acid ester, and can provide the laminated body whose copolymerization ratio (methyl methacrylate / acrylic acid ester) is 80/20-99.5 / 0.5.

Description

Laminate comprising polycarbonate resin

The present invention relates to a laminate comprising a polycarbonate resin used as a mobile terminal display member such as a liquid crystal display cover or a sub display. In particular, preferred embodiments of the present invention are polycarbonate resin laminates for portable terminal display members such as liquid crystal display covers or sub-displays, such as liquid crystal display covers or sub-displays, which have excellent surface hardness, impact resistance and weather resistance. The present invention relates to a laminate comprising a polycarbonate resin for a mobile terminal display member such as a liquid crystal display cover or a sub display having a hardness.

Polycarbonate resin is widely used as a structural material to replace glass because of its excellent transparency, impact resistance, heat resistance, freedom of processing, and light weight, and is widely used as a meter cover, liquid crystal display cover, and window glass for electric, electronic and OA devices. It is widely used in automobiles, sun roofs, instrument covers, and building materials, such as roofing materials and window glass for mining. However, since the polycarbonate resin has low surface hardness and insufficient surface characteristics such as low reflectivity, its use is limited. In addition, in recent years, miniaturization, light weight, high performance, and low price of various devices and devices have been progressed, and the conditions for use of resin molded products including liquid crystal display covers have become more stringent. There is a strong demand for resin materials.

In order to cope with such strict demands, for example, a transparent resin plate having a UV coating film on the surface of the transparent resin plate and a retardation film on the back side is proposed as a liquid crystal display cover (see Japanese Patent Application Laid-Open No. 2000-321993). Although there is no description regarding the material and impact resistance of a transparent resin plate, it was low in practical use. There is also a proposal to use a polycarbonate resin having excellent impact resistance and visibility as a protective cover of a liquid crystal display device (see Japanese Patent Application Laid-Open No. 2001-134196), but there is no description of surface hardness. It was low in practicality. In addition, a proposal to use a polycarbonate resin plate or an acrylic resin plate to cover a liquid crystal display device of a portable communication device and to visually see the display contents (see Japanese Patent Application Laid-Open No. 2002-232542). Even in this case, there was no description of the use of a coextruded laminate of polycarbonate resin and acrylic resin having a surface hardness, impact resistance, and specific thickness, and the practicality was poor. In addition, there have been proposals (see Japanese Patent Application Laid-Open No. 2004-130540) regarding a method for producing a polycarbonate resin laminate coated with a cured coating having excellent impact resistance, but the pencil hardness is not an evaluation target. In other words, the pencil hardness was unsuitable for the required use. Furthermore, a scratch resistant acrylic film suitable for a display window protection plate of a portable information terminal is proposed to be subjected to a hard coat treatment on an acrylic film containing an acrylic resin layer in which rubber particles are dispersed in methacryl resin (Japanese Patent Laid-Open No. 2004-143365). See Japanese Patent Publication No. However, although the hard coat treatment was performed on the acrylic layer containing the rubber particles, the pencil hardness was insufficient when the pencil hardness was measured, compared to the acrylic containing no rubber particles. Moreover, when the laminated body of the acryl layer containing a rubber particle and the acryl layer containing no rubber particle was used, there existed a subject that impact resistance was inadequate. From the present situation as described above, it is strongly desired to provide a resin material excellent in surface hardness, particularly pencil hardness, impact resistance, and weather resistance, suitable as a liquid crystal display cover or a portable terminal display member.

DISCLOSURE OF INVENTION

SUMMARY OF THE INVENTION The problem to be solved by the present invention is a liquid crystal display cover or mobile terminal having a high pencil hardness that is not attainable with a laminate comprising a polycarbonate resin having excellent surface hardness, impact resistance and weather resistance, in particular a general polycarbonate resin plate. It is to provide a laminate comprising a polycarbonate resin suitable for the display member.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said subject, this inventor controls the thickness of the layer containing the acrylic resin which comprises the laminated body containing a polycarbonate resin, and the total thickness of the laminated body to a specific range, By hard-coat treatment on a layer comprising an acrylic resin or a layer comprising an acrylic resin and a substrate containing a polycarbonate resin, a polycarbonate resin suitable for a liquid crystal display cover in which surface hardness, in particular pencil hardness and impact resistance are balanced It discovered that the laminated body containing is obtained and came to complete this invention.

One embodiment of the present invention is a laminate having a substrate containing a polycarbonate resin and a layer containing an acrylic resin, wherein the layer containing the acrylic resin is coextruded on the surface of the substrate containing the polycarbonate resin. Formed, the thickness of the layer containing this acrylic resin is 20-120 micrometers, the total thickness of the laminated body is 0.3-1.5 mm, and the surface of the layer containing this acrylic resin is hard-coat-processed, An acrylic resin is a copolymer of methyl methacrylate and acrylic acid ester, and is a said laminated body whose copolymerization ratio (methyl methacrylate / acrylic acid ester) is 80/20-99.5 / 0.5.

Preferred embodiment of this invention is the laminated body which laminated | stacked the layer containing the acrylic resin of 10-30 micrometers in thickness on the back surface of the base material containing the said polycarbonate resin. Moreover, another preferable embodiment of this invention is the laminated body which laminated | stacked the hard-coat film which a crack does not generate | occur | produce on the back surface of the base material containing the said polycarbonate resin under the stress represented by following formula (1).

σ: stress (Kg / cm 2)

t: total sheet thickness (cm)

Moreover, another preferable embodiment of this invention laminated | stacked the hard-coat film which a crack does not generate | occur | produce on the layer containing the acrylic resin on the back surface of the said base material containing the said polycarbonate resin under the stress represented by said Formula (1). It is a laminated body. Moreover, another preferable embodiment of this invention is a laminated body in which the said acrylic resin contains 0.005-3 weight% of ultraviolet absorbers. Moreover, another preferable embodiment of this invention is a laminated body whose viscosity average molecular weights of the base material containing the said polycarbonate resin are 22,500-25,000.

Another embodiment of the present invention is a liquid crystal display cover having any one of the above-mentioned laminates, wherein the liquid crystal used as an outer side a layer containing an acrylic resin laminated on the surface of a substrate containing the polycarbonate resin. Display cover.

Another embodiment of the present invention is a mobile terminal display member having any one of the above-mentioned laminates, wherein the layer containing an acrylic resin laminated on the surface of a substrate containing the polycarbonate resin is used as an outer side. The portable terminal display member.

According to the present invention, the thickness of the layer containing the acrylic resin constituting the laminate comprising the polycarbonate resin and the total thickness of the laminate are controlled to a specific range, and the layer phase or acrylic resin containing the acrylic resin is further controlled. By carrying out the hard-coat process on the layer containing and the base material containing polycarbonate resin, the laminated body containing polycarbonate resin suitable for the liquid crystal display cover and portable terminal member which balanced the surface hardness and impact resistance can be manufactured.

Brief description of the drawings

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows the relationship between L (the length of an arbitrary chord) used in calculating stress (sigma), and delta (the length of the repair line drawn toward an arc from the center of an arbitrary choice chord).

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in more detail.

The polycarbonate resin of the present invention is obtained by an interfacial polymerization method of an aromatic dihydroxy compound or a small amount of polyhydroxy compound and phosgene or transesterification of the aromatic dihydroxy compound and a diester of carbonic acid. As a thermoplastic polycarbonate polymer which may be branched by reaction, the carbonate ester polymer which uses bisphenol A as a main raw material is used, for example. From the viewpoint that the molecular weight of the polycarbonate resin to be used is capable of producing a sheet by ordinary extrusion molding, the viscosity average molecular weight is 15,000 to 40,000, preferably 20,000 to 35,000, and more preferably 22,500 to 25,000. . Various additives generally used may be added to the polycarbonate resin, and examples of the additives include antioxidants, colorants, ultraviolet absorbers, light diffusing agents, flame retardants, mold release agents, lubricants, antistatic agents, and pigments. .

The acrylic resin of the present invention is preferably a copolymer of methyl methacrylate with acrylic esters such as methyl acrylate or ethyl acrylate, and the copolymer composition and molecular weight may be appropriately selected according to coextrusion conditions. Preference is given to 80 to 99.5% of methacrylates and 0.5 to 20% of acrylic esters such as methyl or ethyl acrylate.

More preferably, they are 90 to 99% of methyl methacrylate and 1 to 10% of acrylic acid esters.

In addition, an acrylic resin containing a crosslinking component can be used within the range in which extrusion molding is possible and the transparency is not impaired. Although molecular weight is 3-300,000 by weight average molecular weight, it is not limited only to these. The higher the load bending temperature of the acrylic resin, the higher the glass transition temperature, the closer the roll transfer temperature to the roll transfer temperature of the polycarbonate resin, and thus a laminate having excellent roll transfer property and excellent appearance is obtained. Therefore, the load deflection temperature of the acrylic resin is preferably 90 ° C or higher, preferably 95 ° C or higher, and more preferably 100 ° C or higher. In order to ensure high pencil hardness, it is preferable that an acrylic resin does not contain a rubber component substantially.

The method for producing an acrylic resin is generally classified into emulsion polymerization, suspension polymerization, and continuous polymerization, but the acrylic resin used in the present invention may be used in any polymerization method. Preferably it is manufactured by suspension polymerization method or continuous polymerization method, More preferably, it is manufactured by continuous polymerization method. The continuous production method is divided into a continuous block polymerization method and a continuous solution polymerization method. In the present invention, the acrylic resin obtained by any production method can be used.

The laminated body containing the polycarbonate resin of this invention has a base material containing polycarbonate resin, the layer containing an acrylic resin, and a hard coat layer. If necessary, a low reflection treatment layer may be formed, and the total thickness of the laminate (the sum of the base material containing the polycarbonate resin and the at least one layer containing the acrylic resin and the hard coat layer) is 0.3 to 1.5 mm, preferably Is 0.4-1.5 mm. The thickness of the layer containing acrylic resin laminated | stacked on the single side | surface of the base material containing polycarbonate resin is 20-120 micrometers, Preferably it is 40-100 micrometers, More preferably, it is 40-80 micrometers. If the total thickness of the laminate including the polycarbonate resin is less than 0.3 mm, the warp against the load from the outside becomes large, and if the total thickness exceeds 1.5 mm, the thickness and weight of the liquid crystal product are inhibited. Moreover, when the thickness of the layer containing acrylic resin is less than 20 micrometers, pencil hardness is low, and when it exceeds 120 micrometers, since the impact resistance of a laminated body falls, it is unpreferable.

The layer containing the acrylic resin of 10-30 micrometers thickness can be laminated | stacked on the back surface of the base material containing the polycarbonate resin which has not laminated | stacked the layer containing the said acrylic resin. By the presence of a layer containing acrylic resin on both sides, width can be imparted to the molding conditions in extrusion molding. In the case of hard coating on both sides, there is no need to use paint separately from the front and back. When the thickness of the layer containing this acrylic resin exceeds 30 micrometers, impact resistance falls, and when it is less than 10 micrometers, it is difficult to aim at thickness uniformity. Preferably, the thickness of the layer containing this acrylic resin is 15-25 micrometers.

In acrylic resin, it is preferable to add 0.005-3.0 weight% of ultraviolet absorbers for the purpose of maintaining weather resistance for a long time. In addition, in order to prevent the thermal deterioration of an acrylic resin at the time of coextrusion molding, you may add antioxidant and a coloring agent. Antioxidant is preferably added to 0.01 to 3% by weight based on the acrylic resin. The coloring inhibitor can be added in an amount of 0.01 to 3% by weight based on the acrylic resin. When the addition amount of the sum total of a ultraviolet absorber, antioxidant, and a coloring agent is less than 0.1 weight%, sufficient weather resistance may not be shown. Moreover, even if it adds more than 5 weight%, not only the improvement of weather resistance can be expected, but these additives may cause bleed-out and cause whitening, and may also reduce adhesiveness or impact strength.

As a ultraviolet absorber added to the layer containing these acrylic resins, a benzotriazole type, a benzophenone type, a salicylic acid phenyl ester type, and a triazine type ultraviolet absorber are mentioned. As a benzotriazole type ultraviolet absorber, 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3, 5-bis ((alpha), (alpha)-dimethylbenzyl) phenyl] -2H- Benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylenebutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like, and examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Examples of hydroxy-4-methoxy-4'-chlorobenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like can do. As the salicylic acid phenyl ester ultraviolet absorber, pt-butylphenyl salicylic acid ester and the like can be exemplified. As the triazine ultraviolet absorber, 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl)- 1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2- Hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2, 4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5 -Triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyethoxy) -1,3,5-triazine, and the like, but are not limited thereto, and generallyIt can include the available ultraviolet absorbers and the like.

As antioxidants and coloring agents added to the layer containing these acrylic resins, various antioxidants and coloring agents described in catalogs such as Ciba Specialty Chemicals Co., Sumitomo Chemical Industry Co., Ltd., Asahi Denka Co., Ltd. It is possible to use. Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 2,2'-methylenebis (4- Ethyl-6-t-phenol), 3,3 ', 3 ", 5,5', 5" -hexa-t-butyl-a, a ', a "-(mesitylene-2,4,6-tri Yl) tri-p-cresol, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], 2,6-di-t-butyl-4- [4,6-bis (octylthio) -1,3,5-triazine-2 -Ylamino] phenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3 -(3,5-di-t-butyl-4-hydroxyphenylpropionamide), 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3 , 5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-t-butyl-3-hydroxy-2,6-xylyl) methyl ] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, diallyl-3,3'- thiodipropionate, pentaerythritol And trikis (3-laurylthiopropionate), etc. Examples of the coloring inhibitor include tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, 4,4'-thiobis (3-6- t-butylphenol), thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], trisnonylphenyl phosphite, triphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, etc. Moreover, although PEP4C, PEP8, PEP24G, PEP36, HP-10 etc. which were described in the Asahi Denka Industries Co., Ltd. catalog are possible, It is limited to these. No. It is also possible to add a sterically hindered amine compound (HALS) or the like added for the purpose of improving the weather resistance of the acrylic resin.

The laminated body which laminated | stacked the layer containing acrylic resin on the surface of the base material containing polycarbonate resin is manufactured by the following co-extrusion. That is, it consists of one main extruder which extrudes a polycarbonate resin, and the sub extruder which extrudes the acrylic resin which comprises a coating layer, and a sub extruder is employ | adopted smaller than a main extruder normally. The temperature condition of the main extruder is usually 230 to 290 ° C, preferably 240 to 280 ° C, and the temperature condition of the sub-extruder is usually 220 to 270 ° C, preferably 230 to 260 ° C. Moreover, in order to remove the foreign material in resin, it is preferable to provide a polymer filter upstream from the dice | dies of an extruder.

As a method of laminating two kinds of molten resins, well-known methods, such as a multi-manifold system and a feed block system, can be used. In the case of a multi-manifold die, the molten resin laminated in this die is molded into a sheet shape inside the die, and then flows into a shaping roll (polishing roll) whose surface is mirrored to form a bank. This sheet-like molded object is mirror-finished and cooled during the passage of the forming roll, and a laminate is formed. The molten resin laminated in the feed block is introduced into a sheet forming die such as a T die and molded into a sheet shape, followed by surface finishing and cooling with a forming roll to form a laminate. Moreover, as temperature of die | dye, it is 250-320 degreeC normally, Preferably it is 270-300 degreeC, and as a shaping | molding roll temperature, it is 100-190 degreeC normally, Preferably it is 110-180 degreeC. A roll can use a vertical roll or a horizontal roll suitably.

The hard coat treatment performed on the surface of the layer containing the acrylic resin in the laminate produced as described above laminates the hard coat layer cured by thermosetting or active energy ray in order to improve scratch resistance. As an example of the coating material hardened | cured using an active energy ray, the resin composition which added the photoinitiator as a curing catalyst to the resin composition which becomes single or multiple, such as monofunctional or polyfunctional acrylate monomer or oligomer, is mentioned. Examples of the thermosetting resin paint include polyorganosiloxanes and crosslinked acrylics. Such a resin composition may be marketed as a hard coat agent for acrylic resins or polycarbonate resins, and may be appropriately selected by adding a titration with a painting line.

To these paints, in addition to organic solvents, various stabilizers such as ultraviolet absorbers, light stabilizers and antioxidants, surfactants such as leveling agents, antifoaming agents, thickeners, antistatic agents and antifogging agents may be appropriately added. .

In addition, the hard coat process performed on the back surface of the base material containing the polycarbonate resin which has not coextruded the laminated body is performed in order to improve scratch resistance, and laminates the hard coat layer hardened | cured by the active energy ray. As an example of the coating material hardened | cured using an active energy ray, the resin composition which added the photoinitiator as a curing catalyst to the resin composition which becomes single or multiple, such as a monofunctional or polyfunctional acrylate monomer or oligomer, is mentioned. Examples of the thermosetting resin paint include polyorganosiloxanes and crosslinked acrylics. Such a resin composition is marketed as a hard coat agent for acrylic resins or polycarbonate resins, and may be appropriately selected by adding a titration with a coating line.

To these paints, various stabilizers such as ultraviolet absorbers, light stabilizers, antioxidants, surfactants such as leveling agents, antifoaming agents, thickeners, antistatic agents, and antifogging agents may be appropriately added to the paints as necessary.

As an example of the paint hardened | cured using an active energy ray to the layer containing an acrylic resin, the 6-functional urethane acrylate oligomer which can copolymerize with 2-80 weight% of bifunctional (meth) acrylate type compounds with a weight average molecular weight of 300 or less. What added 1-10 weight part of photoinitiators (B) with respect to 100 weight part of photopolymerizable compositions (A) used as 20-98 weight% is mentioned.

As a specific example of the bifunctional (meth) acrylate type compound of molecular weight 300 or less, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol diacrylate, 1,6-hexane Diol di (meth) acrylate, 2- (2'-vinyloxyethoxy) ethyl (meth) acrylic acid, 1, 4- butanediol oligoacrylate, etc. can be illustrated.

Moreover, as a specific example of a 6 functional urethane acrylate oligomer, EB-220 by Daicel Scitech Co., Ltd. UN-3320HC, Negami Co., Ltd. UN-3320HA, Japan Synthetic Chemicals UV-7600B, Japan Synthetic Chemicals UV -7640B and the like can be exemplified.

As a specific example of a photoinitiator (B), what is generally known can be used. Specifically, benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, azobisisobutyronitrile, benzoyl peroxide, etc. are mentioned.

As a specific example which hardens using a thermosetting resin paint to the layer containing an acrylic resin

1) 100 parts by weight of organotrialkoxysilane (C) represented by the following formula (2);

(Wherein R ¹ represents a substituent or an unsubstituted monovalent hydrocarbon group, R ² represents an alkyl group)

2) To 100 parts by weight of the composition comprising 50 to 200 parts by weight of a colloidal silica (D) solution having a silicic anhydride content of 10 to 50% by weight and a particle diameter of 4 to 20 nm,

3) The composition which mix | blended 1.0-5.0 weight part of amine carboxylate and / or quaternary ammonium carboxylate (E) is mentioned.

R ¹ in the organotrialkoxysilane (C) represented by the formula (2) is a substituent having 1 to 8 carbon atoms or an unsubstituted monovalent hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, n-butyl group , alkyl group such as i-butyl group, sec-butyl group, n-hexyl group, n-heptyl group, other γ-chloropropyl group, vinyl group, 3,3,3-trifluoropropyl group, γ-glycid Doxypropyl group, (gamma)-methacryloxypropyl group, (gamma)-mercaptopropyl group, a phenyl group, 3, 4- epoxycyclohexyl ethyl group, etc. are mentioned. In addition, R <^2> in organotrialkoxysilane (C) is a C1-C5 alkyl group, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group etc. are mentioned.

Specific examples of these organotrialkoxysilanes (C) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyl Trimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimeth Methoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrie Methoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxy Cyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n -Propyl diethoxysilane, di-i-propyldimethoxysilane, di-i-propyl diethoxysilane, diphenyldimethoxysilane, diphenyl diethoxysilane, etc. are mentioned, Preferably tetramethoxysilane and tetra Ethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane.

The colloidal silica (D) which comprises the said composition contains 10-50 weight% of silicic anhydrides, and the average particle diameter of colloidal silica is 4-20 nm. The dispersing agent of colloidal silica (D) may be water or an organic solvent, further hydrophilic organic solvents (for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol mono Ethylene glycol derivatives, such as butyl ether and ethylene glycol monoethyl ether, diethylene glycol derivatives, such as diethylene glycol and diethylene glycol monobutyl ether; diacetone alcohol etc.) The mixed solvent of 1 or more types and water can be used. . Among these aqueous solvents, water or a water-methanol mixed solvent is preferable in view of dispersion stability and drying property of the dispersion medium after coating.

As a product in which colloidal silica is dispersed in a basic aqueous solution, Nissan is dispersed in Nissan Chemical Co., Ltd. Snowtex 30, Snowtex 40, Shokubai Chemical Co., Ltd., Cataloid S30, Cataloid S40, Acidic aqueous solution. Nissan Chemical Co., Ltd. MA-ST, IPA-ST, NBA-ST, IBA-ST, EG-ST, XBA-ST, NPC- ST, DMAC-ST and the like.

As amine carboxylate and / or quaternary ammonium carboxylate (E), dimethylamine acetate, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, trimethylbenzylammonium acetate, tetramethylammonium acetate, tetra- n-butylammonium acetate, tetraethylammonium acetate, 2-hydroxyethyltrimethylammonium acetate, etc. are mentioned.

As an example of the paint hardened | cured using an active energy ray on the back surface of the base material containing the polycarbonate resin in which an acrylic resin is not co-extruded, 20-60 weight% of 1, 9- nonane diol diacrylates (b1), UV curable resin, characterized in that 1 to 10 parts by weight of a photopolymerization initiator (G) is added to 100 parts by weight of the photopolymerizable composition (F), which is 40 to 80% by weight of the other compound (b2) copolymerizable with (b1). A coating composition is mentioned.

As another compound (b2) which makes 1,9-nonanediol diacrylate (b1) an essential component, and is copolymerizable with (b1), a bifunctional or more than one polyfunctional (meth) acrylate monomer, and a bifunctional or more than polyfunctional urethane ( Meta) acrylate oligomers (hereinafter referred to as polyfunctional urethane (meth) acrylate oligomers), and bifunctional or higher polyfunctional polyester (meth) acrylate oligomers (hereinafter referred to as polyfunctional polyester (meth) acrylate oligomers). .], A bifunctional or more than polyfunctional epoxy (meth) acrylate oligomer (henceforth a polyfunctional epoxy (meth) acrylate oligomer.), Etc. are mentioned. (Meth) acrylate monomer and oligomer can be used 1 type (s) or 2 or more types.

As a polyfunctional (meth) acrylate monomer, the monomer which has two or more (meth) acryloyloxy groups in a molecule | numerator is mentioned.

Examples of the bifunctional (meth) acrylate monomers include alkylene glycol di (meth) acrylates, polyoxyalkylene glycol di (meth) acrylates, halogen substituted alkylene glycol di (meth) acrylates, and fatty acid polyols. Di (meth) acrylate, bisphenol A or alkylene oxide adduct di (meth) acrylate of bisphenol F, epoxy di (meth) acrylate of bisphenol A or bisphenol F, etc. are typical, but are limited to these Various things can be used. Specific examples of the bifunctional (meth) acrylate monomer include 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol di (meth). ) Acrylate, polypropylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, etc. are mentioned.

Examples of the trifunctional or higher (meth) acrylate monomers include trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, pentaerythritol tetraacrylate, and the like. have.

As a polyfunctional urethane (meth) acrylate oligomer, the urethane-ized reaction product of the (meth) acrylate monomer and polyisocyanate which have one or more (meth) acryloyloxy groups and a hydroxyl group in 1 molecule, etc. are mentioned. As a polyfunctional urethane (meth) acrylate oligomer, urethane of the isocyanate compound obtained by making polyol react with polyisocyanate, and the (meth) acrylate monomer which has at least 1 (meth) acryloyloxy group and a hydroxyl group in 1 molecule. Oxidative reaction products.

As a (meth) acrylate monomer which has one or more (meth) acryloyloxy group and a hydroxyl group in 1 molecule used for a urethanation reaction, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) Acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol Tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are mentioned.

As polyisocyanate used for a urethanation reaction, hydrogenated hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and aromatic isocyanates in these diisocyanates. Diisocyanates (for example, diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), diphenyl or triisocyanates such as triphenylmethanetriisocyanate and dimethylenetriphenyltriisocyanate, or diisocyanate The polyisocyanate obtained by making it multiply is mentioned.

As polyols used for the urethanation reaction, polyester polyols, polyether polyols, etc. are generally used in addition to aromatic, aliphatic and alicyclic polyols. Usually, as an aliphatic and alicyclic polyol, 1, 4- butanediol, 1, 6- hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylol ethane, trimethylol propane, dimethylol heptane, dimethylol propionic acid, dimethylol Butyric acid, glycerin, hydrogenated bisphenol A, and the like.

As polyester polyol, it is obtained by the dehydration condensation reaction of the said polyol and polybasic carboxylic acid (anhydride). Specific examples of the polybasic carboxylic acid include succinic anhydride, adipic acid, maleic anhydride, trimellitic anhydride, hexahydro phthalic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and the like. Can be. Moreover, as polyether polyol, polyoxyalkylene modified polyol obtained by reaction of the said polyol or phenols and alkylene oxide is mentioned besides polyalkylene glycol.

In addition, a polyfunctional polyester (meth) acrylate oligomer is obtained by dehydration condensation reaction of (meth) acrylic acid, a polybasic carboxylic acid (anhydride), and a polyol. Examples of the polybasic carboxylic acid (anhydride) used in the dehydration condensation reaction include (anhydrous) succinic acid, adipic acid, (maleic anhydride), (anhydrous) itaconic acid, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, Hexahydro (phthalic anhydride), (phthalic) phthalic acid, isophthalic acid, terephthalic acid, etc. are mentioned. As the polyol used in the dehydration condensation reaction, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylol propionic acid, dimethylol butyricion Acids, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like.

A polyfunctional epoxy (meth) acrylate oligomer is obtained by addition reaction of polyglycidyl ether and (meth) acrylic acid. Examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl. Ether and the like.

As a photoinitiator used for this invention, what is generally known can be used. Specifically, benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, azobisisobutyronitrile, benzoyl peroxide, and the like, may be mentioned, but is not limited thereto.

The method of apply | coating paint to the surface of the layer containing the acrylic resin of this invention, and the back surface of the base material containing the polycarbonate resin which does not have the layer containing an acrylic resin is a brush, roll, dipping, and flow coating ( Flow, spray, roll coater, flow coater or the method proposed in Japanese Patent Laid-Open No. 2004-130540 can be applied. The thickness of the hard coat layer cured by thermosetting or active energy ray is 1-20 탆, preferably 2-15 탆, more preferably 3-12 탆. If the thickness of the hard coat layer is less than 1 μm, the effect of improving the surface hardness tends to be insufficient. On the contrary, even if the thickness of the hard coat layer exceeds 20 μm, the improvement of the surface hardness is difficult to be further improved, and it is disadvantageous in terms of cost. In some cases.

The hard coat of the back surface of the base material containing polycarbonate resin which is not laminated | stacked by 20-120 micrometers of acrylic resin, ie, the inner surface at the time of using as a product, does not generate a crack under the stress represented by following formula (1). desirable.

σ: stress (Kg / cm 2)

t: total thickness of the sheet (cm)

If cracks are generated under the above stress, cracks may be generated on the inner surface when used as a product, and thus may not withstand use.

The stress was calculated from the stress when the sheet was wound with a round rod of various diameters and left unchanged at room temperature for 48 hours after cracking did not occur.

In addition, calculation formula was defined like following formula (3).

but,

σ: stress (Kg / ㎠)

t: total thickness of the sheet (cm)

E: elastic modulus of polycarbonate (kg / cm 2)

L: Length of the string arbitrarily determined (cm)

δ: length of the line drawn from the center of the chord to the arc

L and δ are shown in FIG. 1.

The hard coat can be given a mat shape having a surface roughness Ra of 0.5 µm or less. By arrange | positioning a mat shape provision surface to a liquid crystal side, the interference pattern which arises when the distance with a liquid crystal member is small becomes difficult to be outstanding. When Ra exceeds 0.5 micrometer, haze value becomes high and an image becomes blurry, and it is unpreferable. Ra is a mean line roughness of the center line, and the value obtained by folding the roughness curve from the center line and dividing the area obtained by the roughness curve and the center line by the length L in µm. Moreover, a nonglare effect is obtained by arrange | positioning a mat shape provision surface in the half liquid crystal side.

The hard coat may be provided with an antireflection layer. As an antireflection layer, it is preferable that a high refractive index layer and a low refractive index layer are laminated | stacked two or more layers so that a low refractive index layer may become the outermost surface. As the high refractive index material constituting the layer is not particularly limited, and for example, there may be mentioned metal oxides such as _{TiO 2, Y 2 O 3,} La 2 O 3, ZrO 2, Al 2 O 3.

The present invention is not limited particularly as a material for forming the low refractive index layer, _{e.g., SiO 2, MgF 2, LiF} , 3NaF? AIF 3, AIF 3, Na 3 AIF can be a metal oxide or a metal fluoride, such as ₆ .

The thickness of the antireflection layer depends on the design of the antireflection layer, but is usually used in the range of the lower limit of 10 nm and the upper limit of 300 nm.

The method for forming the antireflection layer on the hard coat layer is not particularly limited, and for example, known methods such as sputtering, vapor deposition, plasma CVD, and coating can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

The polycarbonate resin, acrylic resin, and ultraviolet absorber used in the examples are shown below.

1. Polycarbonate resin: Mitsubishi Gas Chemical Co., Ltd., Eupyron S-1000, viscosity average molecular weight 24,500.

2. Acrylic resin: Product made by Gureray, parapet HR-1000L, load deflection temperature 101 degreeC.

3. UV absorber: Tinuvin 1577 (trade name), manufactured by Ciba Specialty Chemicals, Inc. [Compound name: 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5 -Triazines.

4. The composition for ultraviolet curable resin coating to apply | coat to the layer containing acrylic resin becomes a raw material described below.

EB-220: 6-functional urethane acrylate oligomer (made by Daicel Scitech Co., Ltd.)

# 260: 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

Initiator: Ciba Specialty Chemicals Co., Ltd. I-184 [Compound name: 1-hydroxy-cyclohexylphenyl ketone]

5. The composition for thermosetting resin coating to apply | coat to the layer containing acrylic resin becomes a raw material described below.

Methyltrimethoxysilane: (manufactured by Shin-Etsu Chemical Co., Ltd.)

Snowtex 30: colloidal silica (made by Nissan Chemical Industries, Ltd.)

Snowtex IBA-ST: colloidal silica (made by Nissan Chemical Industries, Ltd.)

6. The composition for ultraviolet curable resin coating to apply | coat to the base material containing polycarbonate resin becomes a raw material described below.

# 260: 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

U6HA: 6 functional urethane acrylate oligomer (made by Shin-Nakamura Chemical Co., Ltd.)

TAS: Condensate of the molar ratio 1/2/4 of succinic acid / trimethylol ethane / acrylic acid (made by Osaka Organic Chemical Industry Co., Ltd.)

APO initiator: trimethyl benzoyl diphenyl phosphine oxide (made by B.S.F Japan)

BNP initiator: benzophenone (made by Wako Pure Chemical Industries, Ltd.)

Ultraviolet absorber: Tinuvin-PS made by Ciba Specialty Chemicals Co., Ltd. [Compound name: 2- (hydroxy-5-tert-butylphenyl) benzotriazole]

The measurement and evaluation of the various physical properties in an Example and a comparative example were performed with the following method.

1) Pencil hardness: It measured by 1 Kg load based on JISK5400.

2) Impact resistance: A 60 mm × 60 mm sample sheet was fixed to a 50 mm φ circular holder, and a steel ball of 38 mm in diameter and 225 g in weight was dropped at a height of 500 mm. The test gave an impact on the surface of the substrate containing the polycarbonate resin up.

UV-curable resin coating production example 1 coated on a layer containing acrylic resin

90 parts of Daicel Scitech Co., Ltd. EB-220 heated to 60 degreeC in the mixing dissolution tank provided with a stirring blade and a temperature control jacket, # 260: 1,9-nonanediol di of Osaka Organic Chemical Industry Co., Ltd. 10 parts of acrylates, and 3 parts of I-184: 1-hydroxy cyclohexyl phenyl ketone made from Ciba Specialty Chemicals Co., Ltd. were added, and it stirred at 40 degreeC for 1 hour.

Preparation Example 1 of a thermosetting resin coating coated on a layer containing acrylic resin

After mixing 1 part of acetic acid with 100 parts by weight of methyltrimethoxysilane (A), the mixture was cooled in an ice bath and stirred at a temperature of 0 to 10 ° C., followed by Snowtex 30 (trade name Nissan Chemical Industries, Ltd.). the colloidal silica SiO ₂ was added dropwise to 30 wt%, average particle diameter 10 ~ 20 ㎚) 84 parts. After dropping, the temperature was kept at 10 ° C., followed by stirring for 4 hours, and then 84 parts of Snowtex IBA-ST (trade name Nissan Chemical Co., Ltd., 25 to 26 wt%, average particle diameter: 10 to 20 nm) was added dropwise. Then, the mixture was stirred at 20 ° C. for 50 hours for aging. Next, 45 parts of cellosolves, 50 parts of isobutyl alcohols, and 0.02 parts of KP-341 (trade name Shin-Etsu Chemical Co., Ltd. polyoxyalkylene glycol dimethylsiloxane copolymer) were added dropwise at room temperature over 1 hour. Further, 0.02 parts of tetramethylammonium acetate was added dropwise at room temperature over 1 hour as a curing catalyst, and mixed to prepare a paint. After preparation, 10 parts of 2, 4- dihydroxy benzophenones were added as a ultraviolet absorber with respect to 100 parts of resin powder in a paint, and the coating was completed.

UV curable resin coating production example 2 coated on the base material containing polycarbonate resin

Osaka Organic Chemical Industry Co., Ltd. # 260: 40 parts of 1,9-nonanediol diacrylates, Shinnakamura Chemical Industry Co., Ltd. U6HA: 6 functional urethane acryl in a mixed dissolution tank equipped with a stirring blade and a temperature control jacket. 20 parts of condensate of molar ratio 1/2/4 of TAS: succinic acid / trimethylol ethane / acrylic acid, and 20 parts of late oligomers, and APO: trimethyl benzoyl diphenyl phosphine oxide made by ASF Japan To 2.8 parts, Wako Pure Chemical Co., Ltd. BNP: 1.0 part of benzophenone, C. specialty Chemicals Co., Ltd. Tinuvin PS: 2- (hydroxy-5-tert- butylphenyl) benzotriazole 1 It added and stirred at 40 degreeC for 1 hour.

Example 1

As an extruder which extrudes a polycarbonate, it was set as barrel diameter 65mm, screw L / D = 35, and cylinder temperature 270 degreeC. In addition, the extruder which extrudes the acrylic resin which forms a coating layer was set to 32 mm of barrel diameters, L / D = 32 of a screw, and 250 degreeC of cylinder temperature. When melt-extruding two kinds of resins at the same time and laminating them, an acrylic resin (Kuraray Co., Ltd.) is used on one side of a polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name: Eupyron S-1000) using a feed block. First, a brand name: parapet HR-1000L) was laminated. The temperature in the die pad is 260 ° C, and the resin integrated into the die is led to three polishing rolls in a mirror-finished horizontal batch, and the first roll temperature is 110 ° C, the second roll temperature is 140 ° C, and the third roll is The temperature was set at 185 ° C. After forming a bank at the roll interval which flows in for the first time, the roll was passed through 2nd and 3rd times, and the 0.4-mm-thick coextrusion sheet was extruded. At this time, the rotation speed of the main extruder and the sub-extruder was set such that the discharge ratio was main / sub = 340/60. The average thickness of the layer containing the acrylic resin in the coextrusion sheet was 60 µm. The coating film after hardening | curing the coating composition of UV cure resin manufacture example 1 between the acrylic resin surface of the said coextrusion sheet which adjusted surface temperature to 80 degreeC with the hot air circulation dryer, and the 100-micrometer-thick PET film separately prepared, 3-8. After inserting it into a micrometer, and crimping | bonding, using a high pressure mercury lamp of 80 W / cm of output density, it irradiates and hardens | cures an ultraviolet-ray on the conditions of a conveyor speed of 3.0 m / min at the position of 12 cm under a light source, and hardens PET film after hardening It peeled and obtained the laminated body containing polycarbonate resin. Table 1 shows the evaluation results of the produced laminate.

[Example 2]

As an extruder which extrudes a polycarbonate, it was set as barrel diameter 65mm, screw L / D = 35, and cylinder temperature 270 degreeC. In addition, the extruder which extrudes the acrylic resin which forms a coating layer was set to 32 mm of barrel diameters, L / D = 32 of a screw, and 250 degreeC of cylinder temperature. When melt-extruding two kinds of resins at the same time and laminating them, an acrylic resin (Kuraray Co., Ltd.) is used on one side of a polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name: Eupyron S-1000) using a feed block. First, a brand name: parapet HR-1000L) was laminated. The flow path of the feed block was such that layers containing acrylic resin were laminated on both sides, and the choke bar opening degree was adjusted in the feed block so that the thickness of the layer containing acrylic resin on the front and back was 3/1. The temperature in the die pad is 260 ° C, and the resin integrated into the die is led to three polishing rolls in a mirror-finished horizontal batch, and the first roll temperature is 110 ° C, the second roll temperature is 140 ° C, and the third roll is The temperature was set at 185 ° C. After forming a bank at the roll interval which flows in first, it passed the roll 2 and 3, and extruded the 0.8 mm-thick coextrusion sheet. At this time, the rotation speed of the main extruder and the sub-extruder was set so that discharge volume ratio might be main / sub = 720/80. In addition, the average thickness of the layer containing the acrylic resin in the 0.8 mm thick coextrusion sheet was 60 µm on one side and 20 µm on the other. After coating the coating material of the thermosetting resin coating manufacture example 1 which coat | covers the layer containing an acrylic resin on both surfaces of this coextrusion sheet, it air-dried for 15 minutes at room temperature, and 60 in the hot air circulation dryer heated at 120 degreeC. Cured for minutes.

Example 3

As an extruder which extrudes a polycarbonate, it was set as barrel diameter 65mm, screw L / D = 35, and cylinder temperature 270 degreeC. In addition, the extruder which extrudes the acrylic resin which forms a coating layer was set to 32 mm of barrel diameters, L / D = 32 of a screw, and 250 degreeC of cylinder temperature. When melt-extruding two kinds of resins at the same time and laminating them, an acrylic resin (Kuraray Co., Ltd.) is used on one side of a polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name: Eupyron S-1000) using a feed block. First, a brand name: parapet HR-1000L) was laminated. The temperature in the die pad is 260 ° C, and the resin integrated into the die is led to three polishing rolls in a mirror-finished horizontal batch, and the first roll temperature is 110 ° C, the second roll temperature is 140 ° C, and the third roll is The temperature was set at 185 ° C. After forming a bank at the roll interval which flows in first, rolls 2 and 3 were passed and the 1.5-mm-thick coextrusion sheet was extruded. At this time, the rotation speed of the main extruder and the sub-extruder was set such that the discharge ratio was main / sub = 1420/80. The average thickness of the layer containing the acrylic resin in the 1.5 mm thick coextrusion sheet was 80 µm. The coating film after hardening | curing the coating composition of UV cure resin manufacture example 1 between the acrylic resin surface of the said coextrusion sheet which adjusted surface temperature to 80 degreeC with the hot air circulation dryer, and the 100-micrometer-thick PET film separately prepared, 3-8. After inserting it into a micrometer, and crimping | bonding, using a high pressure mercury lamp of 80 W / cm of output density, it irradiates and hardens | cures an ultraviolet-ray on the conditions of a conveyor speed of 3.0 m / min at the position of 12 cm under a light source, and hardens PET film after hardening Peeled off. Furthermore, the coating composition of UV cure resin manufacture example 2 was apply | coated and hardened | cured also on the PC surface in which acrylic resin is not laminated | stacked, and the laminated body containing polycarbonate resin was obtained. Table 1 shows the evaluation results of the produced laminate.

Example 4

As an extruder which extrudes a polycarbonate, it was set as barrel diameter 65mm, screw L / D = 35, and cylinder temperature 270 degreeC. In addition, the extruder which extrudes the acrylic resin which forms a coating layer was set to 32 mm of barrel diameters, L / D = 32 of a screw, and 250 degreeC of cylinder temperature. When melt-extruding two kinds of resins at the same time and laminating them, an acrylic resin (Kuraray Co., Ltd.) is used on one side of a polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name: Eupyron S-1000) using a feed block. First, a brand name: parapet HR-1000L) was laminated. The flow path of the feed block was such that the layer containing acrylic resin was laminated on both sides, and the choke bar opening degree was adjusted in the feed block so that the thickness of the layer containing acrylic resin on the front and back was 4/1. The temperature in the die pad is 260 ° C, and the resin integrated into the die is led to three polishing rolls in a mirror-finished horizontal batch, and the first roll temperature is 110 ° C, the second roll temperature is 140 ° C, and the third roll is The temperature was set at 185 ° C. After forming a bank at the roll interval which flows in first, rolls 2 and 3 were passed and the 1.5-mm-thick coextrusion sheet was extruded. At this time, the rotation speed of the main extruder and the sub-extruder was set such that the discharge ratio was main / sub = 1400/100. In addition, the average thickness of the layer containing the acrylic resin in the 1.5 mm thick coextrusion sheet was 80 µm on one side and 20 µm on the other. The coating composition described in Production Example 1 of the ultraviolet curable resin coating to be coated on the acrylic resin between the acrylic resin surface of the coextruded sheet whose surface temperature was adjusted to 80 ° C. with a hot air circulation dryer and a 100 μm thick PET film prepared separately. The coating film after curing was inserted into 3 to 8 µm, and after pressing, using a high-pressure mercury lamp with an output density of 80 W / cm, ultraviolet rays were cured under conditions of a conveyor speed of 3.0 m / min at a position of 12 cm under a light source. After the curing, the PET film was peeled off, and both acrylic resin surfaces were subjected to a hard coat treatment. Table 1 shows the evaluation results of the produced laminate.

Example 5

As an extruder which extrudes a polycarbonate, it was set as barrel diameter 65mm, screw L / D = 35, and cylinder temperature 270 degreeC. In addition, the extruder which extrudes the acrylic resin which forms a coating layer was set to 32 mm of barrel diameters, L / D = 32 of a screw, and 250 degreeC of cylinder temperature. When melt-extruding two kinds of resins at the same time and laminating them, an acrylic resin (Kuraray Co., Ltd.) is used on one side of a polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name: Eupyron S-1000) using a feed block. First, a brand name: parapet HR-1000L) was laminated. The temperature in the die pad is set to 260 ° C, and the resin integrated into the die is led to three polishing rolls in a mirror-finished street arrangement, and the first roll temperature is 110 ° C, the second roll temperature is 140 ° C, and the third The roll temperature was set at 185 ° C. After forming a bank at the roll interval which flows in first, rolls 2 and 3 were passed and the 1.5-mm-thick coextrusion sheet was extruded. At this time, the rotation speed of the main extruder and the sub-extruder was set such that the discharge ratio was main / sub = 1465/35. The average thickness of the layer containing the acrylic resin in the 1.5 mm thick coextrusion sheet was 35 μm. The coating film after hardening | curing the coating composition of UV cure resin manufacture example 1 between the acrylic resin surface of the said coextrusion sheet which adjusted surface temperature to 80 degreeC with the hot air circulation dryer, and the 100-micrometer-thick PET film prepared separately is 8-12. After inserting it into a micrometer, and crimping | bonding, using a high pressure mercury lamp of 80 W / cm of output density, it irradiates and hardens | cures an ultraviolet-ray on the conditions of a conveyor speed of 3.0 m / min at the position of 12 cm under a light source, and hardens PET film after hardening Peeled off. Table 1 shows the evaluation results of the produced laminate.

Comparative Example 1

A laminate including polycarbonate resin was prepared in the same manner as in Example 1 except that the rotational speed of the main extruder and the sub-extruder was changed so that the discharge amount ratio was main / sub = 390/10 in Example 1, and the evaluation results were obtained. Table 2 shows.

Comparative Example 2

A laminate including polycarbonate resin was prepared in the same manner as in Example 3, except that the rotation rate of the main extruder and the sub-extruder was changed so that the discharge amount ratio was main / sub = 1360/140 in Example 3. Table 2 shows.

The present invention is a laminate comprising a polycarbonate resin used as a mobile terminal display member such as a liquid crystal display cover or a sub display. In particular, a preferred aspect of the present invention is a polycarbonate resin laminate for mobile terminal display members such as liquid crystal display covers or sub-displays having excellent surface hardness, impact resistance and weather resistance, and particularly high pencil hardness that cannot be achieved with general polycarbonate resins. A laminate comprising a polycarbonate resin for a mobile terminal display member such as a liquid crystal display cover or a sub display having

Claims (8)

A laminate having a substrate containing a polycarbonate resin and a layer containing an acrylic resin, wherein a layer containing the acrylic resin is formed on the surface of the substrate containing the polycarbonate resin by co-extrusion, and the acrylic resin is The layer to be included has a thickness of 20 to 120 µm, the total thickness of the laminate is 0.3 to 1.5 mm, and the surface of the layer containing the acrylic resin is hard-coated, and the acrylic resin is methyl methacrylate and It is a copolymer of acrylic ester, copolymerization ratio (methyl methacrylate / acrylic acid ester) is 80/20-99.5 / 0.5, The said laminated body which laminated | stacked the layer containing the acrylic resin of thickness 10-30micrometer on the back surface of the base material containing the said polycarbonate resin. delete delete The method of claim 1, The laminated body which laminated | stacked the hard-coat film | membrane which a crack does not generate | occur | produce on the layer containing the acrylic resin of the back surface of the said polycarbonate resin under a stress represented by following formula (1).

σ: stress (Kg / cm 2) t: total sheet thickness (cm) The method of claim 1, The said acrylic resin contains 0.005 to 3 weight% of ultraviolet absorbers. The method of claim 1, The laminated body whose viscosity average molecular weights of the base material containing the said polycarbonate resin are 22,500-25,000. A liquid crystal display cover having the laminate according to any one of claims 1 and 4 to 6, wherein the layer containing an acrylic resin laminated on the surface of the substrate containing the polycarbonate resin is used on the outside. LCD display cover. A mobile terminal display member having the laminate according to any one of claims 1 and 4 to 6, wherein the layer comprising an acrylic resin laminated on the surface of the substrate containing the polycarbonate resin is used on the outside. The mobile terminal display member.

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